Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/002—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the linkage of the reactive group being alternatively specified
  • C09B62/006—Azodyes
  • C09B62/0064—Azodyes with coupling components containing both hydroxyl and amino groups as directing groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B43/00—Preparation of azo dyes from other azo compounds
  • C09B43/44—Preparation of azo dyes from other azo compounds by substituting amine groups for hydroxyl groups or hydroxyl groups for amine groups; Desacylation of amino-acyl groups; Deaminating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions

Definitions

• the present invention relates to a process for the preparation of reactive azo dyes, starting from maleinylated aminoazo compounds.
• the selectivity of the coupling in the production of azo color substances can be controlled, for example, by parameters such as the temperature and the pH (cf. US Pat. No. 5,350,838).
• DE-A 32 17 224 US-A 4 841 027
• a certain orientation in the coupling is achieved by acylating the amino group of naphthalenesulfonic acid coupling components with an anhydride of a dibasic acid, such as maleic anhydride, before the coupling.
• the aminoazo compounds acylated in this way are then hydrolyzed and temporarily isolated before they are further reacted with reactive components to form reactive dyes.
• a process has now been found for the preparation of reactive azo dyes which, in the form of their free acid, correspond to the formula (I)
• A is the residue of a diazo component, in particular from the benzene or
• X denotes a fiber-reactive heterocyclic radical which is characterized in that maleinylated aminoazo dyes of the formula (IV)
• R 1 and R 2 independently of one another are hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, optionally by substituents such as halogen, in particular F, Cl or Br, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or SO 3 H, substituted arylazo, especially sulfophenylazo.
• n, o and p are independently 0 or 1.
• R 1 and R 2 independently of one another represent hydrogen, chlorine, fluorine, methyl, ethyl, methoxy, ethoxy or 4-sulfophenylazo.
• the compound obtained in the saponification of the maleinylated aminoazo dye of the formula (IV) probably corresponds to the formula (V)
• A represents a benzene derivative of the formula (II) which corresponds to the formula (VII)
• R 1 , R 2 , n, o or p have the meaning given above
• the saponification is generally carried out in an aqueous alkaline solution, preferably at pH ⁇ 10 and temperatures of 60 ° to 105 ° C; alkali or alkaline earth metal hydroxides are used as bases, preferably sodium hydroxide, potassium hydroxide, lithium hydroxide.
• alkali or alkaline earth metal hydroxides are used as bases, preferably sodium hydroxide, potassium hydroxide, lithium hydroxide.
• the saponification in aqueous-acidic solution is of greater importance, preferably at pH values 4 4 and temperatures of 60 ° to 105 ° C.
• mineral acids are used as acids, preferably hydrochloric acid and Sulfuric acid. Further process parameters for saponification can be found, for example, in DE-A 3 217 224.
• Suitable fiber reactive heterocyclic X i.e. those which react with the OH or NH groups of the fiber under dyeing conditions to form covalent bonds are in particular those which have at least one reactive one
• substituents bound to a 5- or 6-membered aromatic-heterocyclic ring for example to a monoazine, diazine or triazine ring, in particular a pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetrical or symmetrical triazine ring, or to such a ring system, which one or more fused aromatic-carbocyclic
• Has rings for example a quinoline, phthalazine, cinnoline, quinazoline, quinoxaline, acridine, phenazine and phenanthridine ring system.
• Fiber-reactive residues from the series of pvrimidines or triazines are particularly suitable.
• the reactive substituents on the heterocycle are, for example, halogen (Cl, Br or F), ammonium including hydrazinium, pyridinium, picolinium, carboxypyridinium, sulfonium, sulfonyl, azido (N 3 ), rhodanido, thiol ether, oxiether, sulfinic acid and sulfonic acid
• X can therefore stand for a radical of the formula
• X-Hal can be mentioned as examples of fiber-reactive radicals
• Ammonia morpholine, aniline, N-methylaniline, N-ethylaniline, o-toluidine, orthanilic acid, metanilic acid, sulfanilic acid, 1, 3-diaminobenzene, 1, 4-diaminobenzene, 2,5-diaminobenzenesulfonic acid, 2,4-diaminobenzenesulfonic acid, 2, 2'-benzidine-disulfonic acid, 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminopropane, 4-aminophenyl-ß-sulfatoethylsulfone, 3-aminophenyl-ß-sulfatoethylsulfone, 2-phenylaminoethyl-2'sulfatoethylsulfone, 2 -Phenylaminoethyl-2'2-sulfatoethyl s
• the preferred triazine dyes which are still to be condensed with HR 3 are obtained by the process according to the invention, where X-Hal is cyanuric chloride or cyanuric fluoride.
• the dyes of the formula I obtained by the process according to the invention, in which X is a radical of the formula XV, in which R 3 is F or Cl is and Y, A and m can have the meaning given above, are preferably doubled if they are reacted with diamines, such as those mentioned for HR 3 , These dyes correspond to the formula
• R is a bivalent diamino residue
• a preferred embodiment of the process according to the invention is characterized in that the compounds of the formula (IV) are obtained in that compounds of the formula (XI) or (XII)
• R 1 , R 2 , n, 0 and p have the broadest meaning given above, diazotized and coupled to compounds of the formula (XIII)
• R 1 , R 2 , n, o and p have the broadest meaning mentioned above
• Aminobenzenesulfonic acids of the general formula (XI) are, for example, orthanilic acid, metanilic acid, sulfanilic acid, 2-amino-4-methylbenzenesulfonic acid, 2-amino-4-methoxybenzenesulfonic acid, 2-amino-4-ethoxybenzenesulfonic acid, 4-amino-3-methoxybenzenesulfonic acid Amino-3-methylbenzenesulfonic acid, 4-amino-5-methoxy-2-methylbenzenesulfonic acid, 2-amino-1, 4-benzenedisulfonic acid, 4-amino-1, 3-benzenedisulfonic acid, 2-amino-5-methyl-1,4- benzenedisulfonic acid, 2-amino-5-methoxy-1, 4-benzenedisulfonic acid, 5- (4-sulfophenylazo) -2-aminobenzenesulfonic acid
• Aminonaphthalenesulfonic acids of the general formula (XII) are, for example, 2-amino-1-naphthalenesulfonic acid, 2-amino-1, 5-naphthalenedisulfonic acid, 2-amino-1, 5,7-naphthalenetrisulfonic acid, 3-amino-2,5,7- naphthalenetrisulfonic acid, 3-amino-1, 5-naphthalenedisulfonic acid, 3-amino-1,5,7-naphthalenetrisulfonic acid
• Aminonaphtholsulfonic acid derivatives of the general formula (XIII) are obtained, for example, by reacting maleic anhydride with, for example, 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid, 4-amino-5-hydroxy-1, 7-naphthalenedisulfonic acid.
• maleic anhydride with, for example, 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid, 4-amino-5-hydroxy-1, 7-naphthalenedisulfonic acid.
• 6-amino-4-hydroxy-2-naphthalenesulfonic acid 7-amino-4-hydroxy-2-naphthalenesulfonic acid
• the reaction is described, for example, in DE-A-33 16 984, DE-A-31 18 657 and in EP A 90 1 14 described
• aminobenzene derivatives of the general formula (XI) or the aminonaphthalene derivatives of the general formula (XII) are diazotized by processes known per se by the action of at least one molar equivalent of sodium nitrite in the presence of at least two molar equivalents of a strong acid
• the formulas given are those of free acid.
• the salts are generally obtained in the preparation, in particular the alkali salts such as sodium, potassium or lithium salts
• the reactive dyes produced in this way are ideal for dyeing and printing natural or synthetic hydroxyl or amide groups
• Substrates such as silk, leather, wool, synthetic polyamide fibers, but in particular cellulosic materials with a fibrous structure such as linen, cellulose, regenerated cellulose and especially cotton
• H-acid (1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid) were dissolved in water under protective gas until neutral at a temperature of 20 ° C. 14.7 g of maleic anhydride were added. Value dropped to 4.5 and kept it constant with soda solution, the temperature was kept by external cooling
• Example 2 instead of the H-acid used in Example 1, an aquimolar was used
• Example of use The pH of the solution of the product of the formula (1) obtained in Example 1 was brought to 1.4 with hydrochloric acid, then the mixture was stirred at 70 ° C. for 45 minutes, during which the maleinyl residue was split off. The solution was cooled to 20 ° C. The pH was brought to 3.7 with sodium carbonate solution. After adding 19.6 g of cyanuric chloride, the pH was kept constant with sodium carbonate solution and the temperature was kept constant by external cooling. After the condensation had ended, 6.1 g of 1,4-diaminobenzene were dissolved in water with hydrochloric acid at pH 6 and added to the suspension obtained above. The mixture was heated to 30 ° C., the pH was brought to 6.5 with sodium carbonate solution and held until the reaction had ended. Finally the pH was brought to 8 with sodium carbonate solution, then the dye solution was evaporated to dryness under reduced pressure. 160 g of a dark red powder were obtained, which contained the dye of the formula (8).

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• 1996
  • 1996-01-25 BR BR9607112A patent/BR9607112A/pt not_active Application Discontinuation
  • 1996-01-25 WO PCT/EP1996/000296 patent/WO1996024637A1/de not_active Ceased
  • 1996-01-25 US US08/875,812 patent/US5872228A/en not_active Expired - Fee Related
  • 1996-01-25 KR KR1019970705397A patent/KR19980702000A/ko not_active Withdrawn
  • 1996-01-25 EP EP96902250A patent/EP0808343B1/de not_active Expired - Lifetime
  • 1996-01-25 CA CA002212143A patent/CA2212143A1/en not_active Abandoned
  • 1996-01-25 DE DE59602000T patent/DE59602000D1/de not_active Expired - Fee Related
  • 1996-01-25 CN CN96191812A patent/CN1173888A/zh active Pending
  • 1996-01-25 CZ CZ972514A patent/CZ251497A3/cs unknown
  • 1996-01-25 JP JP8523929A patent/JPH10513495A/ja active Pending

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